Carbon and graphite articles



' i e 2,980,633 United States Patent ice 1,, 1,

and

( )x C2H4N(R )3)4.;'Y(H0 CR")- 5 M SlllCOIl, tin, lead or zirconiumCARBON AND GRAPHITE ARTICLES R is an alkyl group having from 1 to 4carbon atoms, James 0. Koehler, Parma, Ohio, and Headlee Lamprey, R1 15an alkyl substlmtedalkyl l-P vms f .1 Lewiston, N.Y., assignors to Union(Iarbide Corporacarbons tion, a corporation of New York R is an alkylgroup or substituted alkyl group having 4 r 10t 18 b No Drawing. FiledMar. 5, 1957, Ser. No. 643,913 10 x Q33, 3

8 Claims. Cl. 252-507 Y is a number O YH-x) a a t s (c) Polyhydricalcohol derivatives ,f 1 f f This invention relatesto mixtures ofcomminuted car- 5 N n V I bonaceous materials and'pitch binders, and toshaped arti- M is silicon, tin, lead or zirconium v cles producedtherefrom. R is an alkyl group having from 1 to 4 carbon atoms In theconventional manufacture of carbon articles, Y is a substituted alkylenegroup, aromatic group, hycomminuted carbonaceous materials such as coke,carbon droester group, having from 2 to 8 carbons I black and/orartificial graphite are blended with a rela- 20 z is a small wholenumber ranging from H03 and tivelyjhigh melting point coal tar or pitchbinder to form x isa small whole number. ranging from 'l to 3. what isreferred to as a green mix. In such a mix the These compounds, andmethods of preparing the same, ratio of binder to solid is about 1 to 3.To improve the are disclosed and claimed in our copending applicationsextrusion characteristics of the mix, a small amount of Serial No.578,782, filed April 16, 1956, and Serial No. summer oil, about 4 partsper 100 parts of mix, is usually 629,797, filed December 21, 1956.

added. After extrusion, thefinished carbon article is ob: o Illustrativeof the successful practice of the invention, tained by baking tocarbonizethe binder. Thecarbon testn'iixes were prepared having thefollowing composiarticle may be graphitized, if desired, by further heattreat- -tion: I

ments. ('a)'Control'mix'containing no additive During the heattreatments to which the green" mix is l600 'grams of coke subjected, aconsiderable quantity of volatile matter is 560 grams of '30'mediumpitch having a melting point evolved from thebinder and summer oil. As aresult,-the-- around 130" 1 finished articles, particularly large-sized,fine-grained, (b) Additive mixes graphitic articles, are, marred byfissnresand voids. 1600grams of coke It has occurred to many researchersto reduce the 554 grams of 30 medium pitch binder amount of binder andsummer oil in the mix to avoid such 6 grams of additive flaws. To obtainasatisfactoryimprovementin the quality", "In the. additive-containingmixes the additive content of the shaped articles,,this reduction mustbe such that was l pe rcent of the pitch weight. The mixes were thegreen mix is almost impossible to extrude. There is, pr pared byweighing the coke and pitch, placing them in therefore, a need for ameans of reducing the binder, level covered containers, and heating forone hour at 325' and/or eliminate the need for summer oil incarbonaceous F. (162 C.). The'hot coke pitch and additive were mixes,which means willnot affect the extrusion charplaced in a pre-heatedmixer, and mixed one hour at acteristics of the mix.

The main object of this invention, therefore, is to provide additiveswhich will permit considerable reduction 5 ISOf C. to-l6O C.1 The mixeswere removed from the mixer and allowed'tof'cool. Examination of therespective mixes at this stage indicated that the mixes containing ofbinder level in carbonaceous-green-,mixes,- and will the additives had amuch larger aggregate size, were eliminate the ne d f using s r itherein-i F darker and glossier in appearance than the control mix. isan q y important Object of the invention to P Of more importance, themixes containing the additives ide c r and graphite articles havingimproved q y of the invention were wetter in appearance than the con-:Wing the Presence therein 0f ta n;ste mtrol. To show the effectivenessof the additives of the erivatives.

invention in lowering the'binder content, mixes were These n otheroblects ff m ml flfi 9 prepared as indicated above, but having thefollowing by incorporating with green mixes comprising pornminuted'Composition: a

carbonaceous'particles and pitch binde-r's, fror'nOL'Fper- High lid i ti i g dditiv cent to 5 percent by weight thereof of at least one of the2000- grams of coke following organo-rnetallic compounds. 5 7 gramsl'of30 medium pitch having a'meltingpoint j (a) Metal carboxylates around130 C I 4 ""-"12grains of additive a no Y H s 60. The combined eifect ofsummer oil and of the additives 1 R p s or the invention was examined bypreparing mixes with p r 1 x a the following composition: M Sfiicon, tinorlead J s (d) Additive-011mm R is an alkyl' group or substituted alkylgroup,havingfro p 16,00'gl' ,10 to 18 carbon atoms M 5 Pitch 4 a 1 x Ris an alkyl group having from 1 to 4 carbon atoms 32 gr sofioflhmw v v pI V v These'mixescontainegl the same amounts of pitch and 'x' is a smallwhole number, ranging-from'lto 5 (b) Aminoalcohol derivatives of theformulae: 'j

;. .-ino),n tnc,n,mno, ,n

additive as the additive mixes described previously, plus; -two parts'ofsuirimer oil per parts of coke. The a'dvThe extrusionrates and pressuresfor various nzixes Gauge Pressure Additive" Control 6 '20 1 All themixtures contain coke flour; medium pitch (34 parts pitch/100 flour).The mixes were prepared by mixing the ingredients in a blender at 1501C.lortonehour.

All. additives-are present inenamoimtof 0.3 gram additive/liiiigram s 1of coke.

I Two grams .oi'rzsummer oil/1C0: grams of cake was thequantity ofsummer oil addedto themix. V

This series oi'rods contains 27.5 grams of pitch/100 grams of coke.

' The control .cqntainedmo additives.

Generally the control mixes were too dry to measure their extrusionpressures and rates accurately; the data for the control mixes in TableI are, therefore, approximations.

The effect of summer oil in conjunctions with the additives of theinvention is to decrease extrusion pressures required by percent overthose for the additive mixes, the high soiid'mix extruded .;at .ncarlythe same pressure and ratev as the regular-additive mixes. None of theextruded rods except the control rods showed fissures on visualobservation,and all had a smooth surfaceofrhigh luster,,indicative of a'good quality product.

Table II shows the densities of the greenrods with the exception of thehighsolids mix, all fall withinthe range of 1.62 to 1.67 grams per cc.In the case of'the high solids mix, which.;exhihiteda density of 1.58grams per cc., apparently there was not enough pitch to fill all thevoids in the coke.

3000 C. After each operation the rods were measured, weighed, and theirrespective densities calculated. As

indicated in Table III below, the densities of the calcined rodscontaining the additives of the invention consistently TABLE nDimensionsand properties of the green test rods Dimensions SN STA-2 1 SNSTA SNSTA-O 3 SSTA-.-1 i SST-A-2 7 Weight (gramsL, 68. 39 71. 68 71. 7072. 48 72.129 7 .0. 70 ,0. 770 .0. 768 0. 770 0. 770 3 22 8'32? 8'52?8'???) 8??? e I v J mama (mches) 0. 768 0. 770 ,0. 768 0.770 .0. 772 0.767' 0. 767' 0. 767 0. 771 0. 771 0. 766 0.764 0. 764 0.771 10:767. Avg.Diameterfinches) 0. 767 0. 767- 0.766 0. 770 0. 770 Lenzth (inches) l-75. 792 5. 772 5. 767 5. 773 5.771 Volume (cm. 43.25 43. 70 43. 55 44.05 44.04 Density (gJcmfl) 1. 582 1. 644 1. 646 L645 1. 641

1 These-series of rods contain 27.5 parts of pitch/100 flour and 0.5%additive, based pntotal weight of the mix,;.and weremadr-irom a highsolids type of mix as mix (c) of pageii.

1 All these additives are present in anzamount of 0.3% by weight-oi thetotal mix, and-were made from type (b)-mixes.

' Theseseriesot rods contain summer oil present in to the extent of 2%of the weightoi' the coke, and-were made from type .(d),mixes.

the correct range for good calcined stock.

TABLE III Dimensions and properties of test rods calcined at 1000 C.

-Dlmensions SNSTA-2 SNSTA SNS'IA-O' .SS'IA-l ss'rA-2= Weight (gra ms)61.98 05.11 63. as 64.58 64.78 r v 0. 7,70 0. 759 0. 701 0. s 0. 761 a ff 2- 37a 3- 2722 2722 De 0 755 0. 7771 0.761 0. 759 0. 700 7 1 0. 7540.756 0.759 0,759 0.700 0. 752 0; 752 0. 755 0. 758; 0. 75s 1 0. 7540.700 0. 766 0.1758 0.7 5. 728 5.700 5.754 5.731- 5. "V0lume(cm.).'--41.91 43.06 43:45 42.33 42.

Density (gJcrnJ) 1. 479 1, 2 1. 458 1,524 -1; 526

jirom mix type (c).

' gormn'a ea {These seriesoi rods oonta'ined 27.5 parts of pitch/ flouan oiniixyandiweremade 9 These series'of rods contained34 parts ofpithlifli) flour midlife. additive/100 g."of. rnix(type b) 8 Theseseriesoiro'ds contained 34 parts of pitch/IOOjiiour, '2 gesum megoilllloil-grflour and 0.3 g.'additive/100 Property sNsTA-2i SNSTAMicro-amps. .Q. 5. 25 8:30 Resistivity amps/m1)... 574 363 Coefficientof Thermal E in./ C.X10'.5) L 0.159 U. 156

- The densities for rods graphitized at 3000 C. as indicated in Table IVwere again comparable to densities expected of good specimens.

diol- 1,3 )-silicate, isopropoxy-tri- (Z-ethylhexanediol) -silicate,diisopropoxy-di-(Z-ethylhexanediol-1,3)-silicate, diisopropoxy di(2-ethylhexanediol-1,3)-stannate, di-(tri- TABLE IV Dimensions andproperties of test rods graphitized at 3000 C.

Dimensions SNSTA-Z 1 SNSTA 7 SNSTA-O ss'rA-1 7 SSTA-Z H Weight (grams)60.27 63. a 61. 52 62. 9s 62. 74 0. 746 o. 748 0. 75a 0. 751 0. 763 3'iii 3' $23 8' iii 3' i i, 3' iii v D Diameter (inches) 0. 747 0. 747 0.75a 0. 753 0. 754 o. 747 0. 752 o. 753 0. 753 0. 753 o. 746 0. 74s 0.75a 0. 753 0. 753 Avg. Diameter (inches) 0. 746 0. 749 0. 75a 0. 753 o.753 Volume ems) 40. 97 41.14 41. 96 41.65 41. 7e Length (inches). 5. 7205. 689 5. 750 5.707 5. 722 Density (g./cn1. 1. 47 1. 54 1. 47 1. 51 1.so

1 These series of rods contained 27.5 parts of pitch/100 flour, 0.5part; additive/100 mix (type c). 3 These series of rods contained 34parts pitch/100 flour, 0.3 part additive/100 mix (type b). 8 Theseseries of rods contained 34 parts pitch/100 flour, two parts summeroil/100 flour, 0.3 .part addtive/IOO mix (type d).

The foregoing data indicates that no deleterious effect as regards thedensity or appearance of calcined and graphitic shapes accomapny the useof the additives of the invention to reduce the extrusion pressures andbinder level content of green mixes. n

Graphitized rods above produced were tested for their coefficient ofthermal expansion and electrical resistance. These tests are veryimportant in the determination of electrode quality. As indicated inTable V below, the

coefficients of thermal expansion and the electrical resistiviticsof thesamples all fall in the useable ranges of 0.151 to 0.159 l0- inchesper-inch per C., and 363 to 400 micro amps per inch square,respectively. 1

TABLE V 1 obtained when the additives'of the invention are added afterpercent of the mixing time has elapsed.

The compounds of the invention are efiective in mixes containing bindersother than pitch. Thus coke mixes containing tar and synthetic resinous:binders extruded readily, and produced higher quality extruded stockwhen Electrical resistivity of coe ficients of thermal expansion of testrods graphilized at 3000 C.

SNSTA-O 3 1 These series of rods contain 27.5 parts pitch/ flour,0.5;part additlve/IOO'mix (typec);

I These series of rods mix (type d).

While for the sake of brevity-theinvention'has been in the absencethereof.

described 'mainly by 1 reference to --isopropoxy stearoxy polysilicateand butoxy stearoxy polystannate, the same is 'not tobe construed aslimited thereto, but rather to contemplate the use therein of many othercompounds comprehended within the definitionfland formulae given above,including, ;for example, butoxy stearoxy polysilicate, isopropoxystearoxy polysilicate, isopropoxy perfluorobutyryl polysilicate,isopropoxy perfluoroacetoxy I polysilicate, isopropoxy stearoxypolystannate, isopropoxy .oleoxy polystannate, isopropoxy9,l0.-dibromostearoxy' polysilicate, isopropoxy' benzoxy polysilicate,methyl perfluorobutyryl polysilicate, butoxyoleoxy polysilicate, di

ethoxy di (triethanolamine) silicate, dibutoxy-di-(tri- ,ethanolamine)silicate,.; diisopropoxy di (triethanol- .amine)-silicate,-diethoxy-di-.(p-diethylaminoethoxy)-silicate,diethoxy-di-(triethanolamine)-plumbatc dicthoxydi (triethanolarnine)stannate, diethoxy-dij-(triethanol- 1 amine)-silicate-N-oleate,diethoxy-di-(triethanolamine)- silicate:N,N-dioleate,diisopropoxy-di-(triethanolamine).- silic'ate-N-oleate,;diisopropoxy-di-(triethanolamine)-silicate-N,N-dioleate, vdibutoxy-di-([3-diethylaminoethoxy) silicate N oleate,diethoxy-di-(triethanolamine);plurn-' bate-NN-dioleat'e,tetra(triethanolamine sil icate, adiethpart additive/10d V- Ol3peicen tto 0L4 percentv of additive was presentthan vWhat is claimed is: v I l.A process forproducing shaped carbonaceous articles, which comprisesmixing finely divided carbonaceous particles with an organic binder, andfrom 0.1 perceflt'to 5 percent by weight of at least one additiveselected from the group consisting of the carboxylates; of tin, s iliconand lead, the aminoalcohol and polyhyd'ric alcohol derivatives of tin,lead, silicon and zirconium andmixtures thereof, :and forming theresulting mixture finto predeterminate shape, saidcarb'oxylates havingthe formula:

-- havin from '10 to 18 carbon atoms, M is ametal selected 70 is a smallwhole-number rangingirom 1 to 3; r,

oxy-rdi- (triisopropanolamine silicate, ,diethoxydi-{triisw ,prcpa lmine) si icat eN-olearez 'i'te re'st -et y he an "from the- 'g'roupconsisting ofsilicon, tin and lead, R' is an alkyl group havingfrom l to4 c arbon atoms, and

" said amino alcohols having the formula:

1 ow.)XM(M mmas ita (H ll w) wherein M is ametal selected from thegroupconsisting- I ofsilicon, tin, lead and zirconium, R is an alkylgroup having from 1 to 4 carbon atoms, R is selected from the groupconsisting of the alkyl and substitutedalkyl groups having from 1 to 4carbon atoms, R is a member selected from the group consisting of thealkyl and substituted alkyl groups having from 10 to 18 carbon atoms, xis a number ranging from to 3; Y is a number equal to (4x), and saidpolyhydric alcoholates having the formula:

wherein M is a metal selected from the group consisting of silicon, tin,lead and zirconium, R is analkyl group having from 1 to 4 carbon atoms,Y is a substituted alkylene radical having from 2 to 8 carbons, z is anumber ranging from 1 to 3 and x is a number ranging from 1 to 3. I

2. The process of claim 1, wherein said carbonaceous particles arerelatively large and said additive is added after about 80 percent ofthe mixing time has elapsed.

3. A process for producing shaped baked carbon articles, comprisingcomingling carbonaceous particles with a pitch binder, adding summeroil. to the resulting mix, and from 0.1 percent to 5 percent by weightof an additive selected from the group consisting of the carboxylates oftin, lead and silicon, the aminoalcohols and polyhydricalcoholderivatives of tin, lead, silicon and zirconium, shaping the resultingmix and baking to carbonizesaid binder, said carboxylates having theformula:

wherein, R isa member selected from the group consisting, of the alkyl,and the substituted alkyl radicals having from to 18 carbon atoms, M isa metal selected from the group consisting of silicon, tin and lead, Ris an alkyl group having from 1 to 4 carbon atoms, andx is a small wholenumber ranging from 1 to 3;

said amino alcohols having the formula:

wherein M is a metal selected from the group consisting of silicon, tin,lead and zirconium, R is an alkyl group having'from 1 to 4 carbon atoms,R'.is selected from the group consisting of the alkyl. andsubstitutedialkyl groups having from 1 to 4 carbon atoms, R is a mem g iV wherein R is a member selected from the group, consisting of thealkyl, and the substitutedalkyl radicals having from 10 to 18 carbonatoms,iM-' isa; metal selected from the group consisting of silicon, tinand lead, R is an alltyl group having from 1 to 4 carbon atoms, and x isa small whole'nunrber ranging from 1 to 3;

said amino alcohols having the formula:

wherein M is a metal selected from the group consisting of silicon, tin,lead and zirconium, R is an alkyl group having from 1 to 4 carbon atoms,R is selected from the group consisting of the alkyl and substitutedalkyl groups having from 1 to 4 carbon atoms, R is a member selectedfrom the group consisting of the, alkyl and substituted alkyl groupshaving from 10 to 18 carbon atoms, x is a number ranging from 0 to 3;!is a number equal to (4-x), and said polyhydr'ic alcoholates having theformula:

wherein M is a metal selected from the group consisting of silicon, tin,lead and zirconium, R is' an alkyl group having from 1 to 4 carbon,atoms, Y is a substituted alkylene radical having from 2 to 8' carbons,z. is a number ranging from 1 to 3 and x is a number ranging froml to 3.f

7. A green carbonaceous mix characterized by low extrusion pressures,said mix containing carbonaceous particles, an organic binder, summeroil, and from 0.1

percent to, 5 percent by weight of at least one additive I selectedfromthe group consisting of the carboxylates. of tin, lead and silicon, theamino and polyhydric alcohol derivatives of tin, lead, silicon-andzirconium and mixtures thereof, said carboxylates having the formula:

wherein R is a member selected from the group con-' I said aminoalcohols having the formula:

wherein M is a metal selected from the group consisting of silicon, tin;lead and zirconium,.R is an alkyl group 7 having from-.1 to 4 carbonatoms, R" is'selected from wherein'M. is a metal selected from the groupconsisting V of, silicon, ,tin, lead. and zirconium, R is an alkyl grouphaving from 1 to4 carbon. atoms,Y is a substituted 'alkylene radicalhaving from 2 to 8 carbons, z is a num the group consisting of the alkylandjsubstituted alkyl groups having from I to 4 carbon atoms, R"" is amember selected from the: group consisting" off the alkyl and'substituted'alkyl. groups having from 1 0 to 18 carbon atoms, x is'anumber ranging from 0 to'3; Yis a number 7 equal to (4--x), and saidpolyhydric alcoholates having the formula: v

5. The process of claim 3 wherein the amount of said additive is atleast 0:5v percent by Weight of. said mix.

6. A green carbonaceous mix characterized by low extrusion pressuressaid mix containing carbonaceous.

particleg an organic-binder and from 0.1'percent; to 5 percent by weightof at least one additive-selected from. the group consisting of thecarboxylates oftin, lead and s nonnior ioumcx.

wherein M is a metal selected from the'group consisting of silicon,-tin,lead and zirconiurn, R' is an alkyl group having from Into 4carbonatoms, Y is 'a subst'ituted alkyleneara'dical having from 2 to8 carbons,z is a number rangingfrom *1; to and is'a number ranging 'from I to 3.

silicon, thefamino and. polyhydric -alcohol' derivatives of tin,,lead,silicon and zirconium and mixtures thereof, said. carboxylates havingthc tormnla; i

8. A green carbonaceous imix characterized by low extrusion pressuresand; improvedforming characteristics, said mix containing cominuted"carbonaceous particles, an organic 'binderr selected from the groupconsisting of j tat-and synthetic resins, and at least O.3 percentbyvveight of'rnixojfan additive selected from the group consisting 1,of-thejcarboxylat'esof tin, lead andfsili'comtlije arninoalcohol andpolyhydric alcohol [derivatives or"? tini'vlead,

silicon and zirconium, said carboxylates having the wherein R is amember selected from the group consisting of the alkyl, and thesubstituted alkyl radicals having from 10 to 18 carbon atoms, M is ametal selected from the group consisting of silicon, tin and lead, R isan alkyl group having from 1 to 4 carbon atoms, and x is a small wholenumber ranging from 1 to 3; said amino alcohols having the formula:

( )x z 4 ')2)4 x- 2 wherein M is a metal selected from the groupconsisting of silicon, tin, lead and zirconium,-R is an alkyl grouphaving from 1 to 4 carbon atoms, R is selected from the group consistingof the alkyl and substituted alkyl groups 10 having from 1 to 4 carbonatoms, R" is a member selected from the group consisting of the alkyland substituted alkyl groups having from 10 to 18 carbon atoms, x is anumber ranging from 0 to 3; Y is a number equal to (4-2:), and saidpolyhydric alcoholates having the wherein M is a metal selected from thegroup consisting UNITED STATES PATENTS Peterson Aug. 3, 1 948 Shea et a1Aug. 7, 1951 (SEAL) UNITED STATES PATENT OFFICE EERTIFIQATE OFCORRECTION Patent No,, 2380 633 April 18, 1961 James 00- Koehler et al.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said" Letters Patent. should read ascorrected below a Column 4 line 5 for "conjunctions" read conjunctioncolumns 5 and 6 TABLE V in. the heading thereof, line 1, for "ofh initalics first occurrence read and in italics; same columns 5 and 6 inthe footnotes to TABLE V, the footnote numbered "'3" should appear asfootnote number 2 same TABLE V the footnote numbered 2" should appear asfootnote number 3 column 7 line 21 for "comingling" read comminglingcolumn 8 line 70, for cominuted" read comminuted "o Signed and sealedthis 10th day of October 1961.

Attest;

ERNEST W. SWIDER DAVID L. LADD Attesting Officer v Commissioner ofPatents USCOMM-DC-I

1. A PROCESS FOR PRODUCING SHAPED CARBONACEOUS ARTICLES, WHICH COMPRISESMIXING FINELY DIVIDED CARBONACEOUS PARTICLES WITH AN ORGANIC BINDER, ANDFROM 0.1 PERCENT TO 5 PERCENT BY WEIGHT OF AT LEAST ONE ADDITIVESELECTED FROM THE GROUP CONSISTING OF THE CARBOXYLATES OF TIN, SILICONAND LEAD, THE AMINOALCOHOL AND POLYHYDRIC ALCOHOL DERIVATIVES OF TIN,LEAD, SILICON AND ZIRCONIUM AND MIXTURES THEREOF, AND FORMING THERESULTING MIXTURE INTO PREDETERMINATE SHAPE, SAID CARBOXYLATES HAVINGTHE FORMULA: